Molecular vibrations in the presence of velocity-dependent forces
arXiv:2212.10246 · doi:10.1063/5.0139684
Abstract
A semiclassical theory of small oscillations is developed for nuclei that are subject to velocity-dependent forces in addition to the usual interatomic forces. When the velocity-dependent forces are due to a strong magnetic field, novel effects arise -- for example, the coupling of vibrational, rotational, and translational modes. The theory is first developed using Newtonian mechanics and we provide a simple quantification of the coupling between these types of modes. We also discuss the mathematical structure of the problem, which turns out to be a quadratic eigenvalue problem rather than a standard eigenvalue problem. The theory is then re-derived using the Hamiltonian formalism, which brings additional insight, including a close analogy to the quantum-mechanical treatment of the problem. Finally, we provide numerical examples for the H, HT, and HCN molecules in a strong magnetic field.
References in corpus (8)
- Coupled-cluster theory for atoms and molecules in strong magnetic fields
- Ab-Initio Molecular Dynamics with Screened Lorentz Forces. Part I. Calculation and Atomic Charge Interpretation of Berry Curvature
- Ab-Initio Molecular Dynamics with Screened Lorentz Forces. Part II. Efficient Propagators and Rovibrational Spectra in Strong Magnetic Fields
- Analytic Calculation of the Berry Curvature and Diagonal Born-Oppenheimer Correction for Molecular Systems in Uniform Magnetic Fields
- Electron corrected Lorentz forces in solids and molecules in magnetic field
- Bonding in the helium dimer in strong magnetic fields: the role of spin and angular momentum
- Anisotropic harmonic oscillator in a static electromagnetic field
- Magnetic-Translational Sum Rule and Approximate Models of the Molecular Berry Curvature